EP4683953A1 - Polypropylene resin compositon - Google Patents
Polypropylene resin compositonInfo
- Publication number
- EP4683953A1 EP4683953A1 EP23783446.0A EP23783446A EP4683953A1 EP 4683953 A1 EP4683953 A1 EP 4683953A1 EP 23783446 A EP23783446 A EP 23783446A EP 4683953 A1 EP4683953 A1 EP 4683953A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- measured
- polypropylene resin
- resin composition
- anyone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/002—Organic membrane manufacture from melts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present disclosure relates to polypropylene resin composition
- polypropylene resin composition comprising an ultra- high-molecular-weight propylene homopolymer composition containing at least two homopolymer fractions having different intrinsic viscosity for use in the formation of a microporous membrane having good Gurley permeability, measured according to ISO 5636 and good mechanical properties.
- Microporous membranes made of polymeric materials are used in various applications, for example, filter membranes and separation membranes for medical and industrial use, and separators, such as battery separators and condenser separators.
- separators such as battery separators and condenser separators.
- EP 1 464 669 relates to microporous membrane made substantially with high molecular weight polyethylene or a blend of polyethylene and polypropylene. However the air transmission rate (Gurley permeability) can be improved.
- the present disclosure is directed to a polypropylene resin composition
- a polypropylene resin composition comprising:
- A) from 10 wt% to 70 wt% of a polypropylene homopolymer composition comprising:
- Tl from 30 wt% to 70 wt% of a first propylene homopolymer optionally containing up to 1.0 wt% of ethylene derived units having:
- T2 from 30 wt% to 70 wt% of a second propylene homopolymer optionally containing up to 1.0 wt% of ethylene derived units having:
- melt strength measured according to ISO 16790-2005, at 250°C and applying an acceleration equal to 6 mm/s 2 is higher than 0.070 N;
- the fraction soluble in xylene at 25°C measured according to ISO 16 152 - 2005 is comprised between 6.0 wt% and 2.0wt%;
- the intrinsic viscosity (IV) measured in tetrahydronaphthalene at 135 °C ranges from 10.0 to 4.5 dl/g;
- component B) from 30 wt% to 90 wt% of an organic material selected from: organic acid esters; adipic acid esters, glyceric acid esters; phosphoric acid esters; paraffin; wax; and mineral oil; wherein the sum of the amounts of component A) and component B) in wt% is equal to 100 wt% .
- the present disclosure is directed to a polypropylene resin composition
- a polypropylene resin composition comprising:
- A) from 10 wt% to 70 wt% preferably from 20 wt% to 60 wt%; more preferably from 30 wt% to 57 wt% of a polypropylene homopolymer composition comprising:
- Tl from 30 wt% to 70 wt% ; preferably from 40 wt% to 60 wt%; more preferably from 45 wt% to 55 wt% of a first propylene homopolymer optionally containing up to 1.0 wt% of ethylene derived units having:
- T2 from 30 wt% to 70 wt% preferably from 40 wt% to 60 wt%; more preferably from 45 wt% to 55 wt% of a second propylene homopolymer optionally containing up to 1.0 wt% of ethylene derived units having: - the intrinsic viscosity (IV) measured in tetrahydronaphthalene at 135 °C ranging from 2.0 to 5.5 dl/g; preferably from 2.2 to 5.0 dl/g; more preferably from 2.5 to 4.7 dl/g;
- IV intrinsic viscosity
- melting points are present in the DSC thermogram measured according to ISO 11357-3, 20°C/min; preferably the lower melting point ranges from 135°C to 150°C; the higher melting point, measured according to ISO 11357-3, with heating and cooling rate of 20°C/min; ranges from 155°C to 170°C; preferably from 157°C to 168°C;
- the isotactic pentads mmmm % measured with C 13 NMR as reported in the examples section range from 94.5 mol% to 89.0 mol%; preferably from 93.2 mol % to 90.5 mol %; more preferably form 93.0 mol% to 91.0mol%;
- the fraction soluble in xylene at 25°C measured according to ISO 16 152 - 2005 is comprised between 5.0 wt% and 2.0wt%; preferably comprised between 4.5 wt% and 2.2wt%; more preferably comprised between 3.5 wt% and 2.4 wt%;
- melt strength measured according to ISO 16790-2005 at 250°C and applying an acceleration equal to 6 mm/s 2 is higher than 0.070 N; preferably higher than 0.080 N; more preferably higher than 0.082 N;
- the intrinsic viscosity (IV) measured in tetrahydronaphthalene at 135 °C ranges from 10.0 to 4.5 dl/g; preferably from 9.2 to 5.2 dl/g; more preferably from 8.5 to 5.5 dl/g;
- the propylene homopolymer component A) is not nucleated.
- melt strength of the propylene homopolymer component A) is lower than the melt strength of the propylene homopolymer component A
- the propylene homopolymer component A) shows a polydispersity index, PI, measured according to ISO 6721-10, comprised between 4.5 and 7.5; more preferably between 5.0 and 7.2; more preferably from 5.5 to 7.0.
- the propylene homopolymer component A) shows a tensile modulus ranging from 2100 MPa to 1100 MPa; preferably from 1800MPa, to 1200 Mpa.
- the propylene homopolymer component A) shows a charpy impact test at 23°C ranging from 4.0 kJ/m 2 to 11.0 kJ/m 2 ; preferably from 4.5 kJ/m 2 to 7.5 kJ/m 2 .
- the propylene homopolymer component A) can be prepared by a process comprising polymerizing propylene optionally with ethylene, in the presence of Ziegler-Natta catalysts in two reactors connected in series.
- An essential component of said catalysts is a solid catalyst component comprising a titanium compound having at least one titanium-halogen bond, and an electron-donor compound, both supported on a magnesium halide in active form.
- Another essential component (co-catalyst) is an organoaluminium compound, such as an aluminium alkyl compound. An external donor is optionally added.
- Catalysts having the above mentioned characteristics are well known in the patent literature; particularly advantageous are the catalysts described in US patent 4,399,054 and European patent 45977. Other examples can be found in US patent 4,472,524.
- the solid catalyst components used in said catalysts comprise, as electron-donors (internal donors), compounds selected from the group consisting of ethers, ketones, lactones, compounds containing N, P and/or S atoms, and esters of mono- and dicarboxylic acids.
- succinates particularly suitable electron-donor compounds are esters of succinic acid (succinates)
- succinates Preferably, the succinate present in the solid catalyst component is selected from succinates of formula (I) below [0020] in which the radicals Ri and R2, equal to, or different from, each other are a C1-C20 linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms; and the radicals R3 and R4 equal to, or different from, each other, are Ci- C20 alkyl, C3-C20 cycloalkyl, C5-C20 aryl, arylalkyl or alkylaryl group with the proviso that at least one of them is a branched alkyl; said compounds being, with respect to the two asymmetric carbon atoms identified in the structure of formula (I), stereoisomers of the type (S,R) or (R,S
- Ri and R2 are selected from primary alkyls and in particular branched primary alkyls.
- suitable Ri and R2 groups are methyl, ethyl, n- propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.
- ethyl, isobutyl, and neopentyl are particularly preferred.
- R3 and/or R4 radicals are secondary alkyls like isopropyl, sec- butyl, 2-pentyl, 3 -pentyl or cycloakyls like cyclohexyl, cyclopentyl, cyclohexylmethyl.
- Examples of the above-mentioned compounds are the (S,R) (S,R) forms pure or in mixture, optionally in racemic form, of diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2,3-bis(2- ethylbutyl)succinate, diethyl 2,3 -dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diisobutyl
- Particularly suitable electron- donor compounds are esters of phtalic acid and 1,3- diethers of formula:
- R 1 and R n are the same or different and are Ci-Cis alkyl, C3-C18 cycloalkyl or C7-C18 aryl radicals;
- R 111 and R IV are the same or different and are C1-C4 alkyl radicals; or are the 1,3 -di ethers in which the carbon atom in position 2 belongs to a cyclic or polycyclic structure made up of 5, 6, or 7 carbon atoms, or of 5-n or 6-n' carbon atoms, and respectively n nitrogen atoms and n' heteroatoms selected from the group consisting of N, O, S and Si, where n is 1 or 2 and n' is 1, 2, or 3, said structure containing two or three unsaturations (cyclopolyenic structure), and optionally being condensed with other cyclic structures, or substituted with one or more substituents selected from the group consisting of linear or branched alkyl radicals; cycloalkyl, aryl, aralkyl
- diethers are 2-methyl-2-isopropyl-l,3- dimethoxypropane, 2,2-diisobutyl-l,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-l,3- dimethoxypropane, 2-isopropyl-2-isoamyl-l,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene.
- Suitable electron-donor compounds are phthalic acid esters, such as diisobutyl, dioctyl, diphenyl and benzylbutyl phthalate.
- a MgC12»nROH adduct (in particular in the form of spheroidal particles) wherein n is generally from 1 to 3 and ROH is ethanol, butanol or isobutanol, is reacted with an excess of TiC14 containing the electron-donor compound.
- the reaction temperature is generally from 80 to 120° C.
- the solid is then isolated and reacted once more with TiC14, in the presence or absence of the electron-donor compound, after which it is separated and washed with aliquots of a hydrocarbon until all chlorine ions have disappeared.
- the titanium compound expressed as Ti
- the quantity of electron-donor compound which remains fixed on the solid catalyst component generally is 5 to 20% by moles with respect to the magnesium dihalide.
- the titanium compounds which can be used for the preparation of the solid catalyst component, are the halides and the halogen alcoholates of titanium. Titanium tetrachloride is the preferred compound.
- the reactions described above result in the formation of a magnesium halide in active form. Other reactions are known in the literature, which cause the formation of magnesium halide in active form starting from magnesium compounds other than halides, such as magnesium carboxylates.
- the Al-alkyl compounds used as co-catalysts comprise the Al-trialkyls, such as Al- triethyl, Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO4 or SO3 groups.
- Al-trialkyls such as Al- triethyl, Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic Al-alkyl compounds containing two or more Al atoms bonded to each other by way of O or N atoms, or SO4 or SO3 groups.
- the Al-alkyl compound is generally used in such a quantity that the Al/Ti ratio be from 1 to 1000.
- the electron-donor compounds that can be used as external donors include aromatic acid esters such as alkyl benzoates, and in particular silicon compounds containing at least one Si- OR bond, where R is a hydrocarbon radical.
- silicon compounds are (tert-butyl)2Si(OCH3)2, (cyclohexyl)(methyl)Si (OCH3)2, (cyclopentyl)2Si(OCH3)2 and (phenyl)2Si(OCH3)2 and (1,1,2- trimethylpropyl)Si(OCH3)3.
- 1,3 -diethers having the formulae described above can also be used advantageously. If the internal donor is one of these diethers, the external donors can be omitted.
- the component A) are preferably prepared by using catalysts containing a phthalate as internal donor and (cyclopentyl)2Si(OCH3)2 as outside donor, or the said 1,3-diethers as internal donors.
- the polymerization is generally carried out at temperatures of from 20 to 120°C, preferably of from 40 to 80°C.
- the operating pressure is generally between 0.5 and 5 MPa, preferably between 1 and 4 MPa.
- the operating pressure is generally between 1 and 8 MPa, preferably between 1.5 and 5 MPa.
- Hydrogen is typically used as a molecular weight regulator.
- the polymerization can be in gas phase or in slurry or in solution. In one or more reactors. Preferably the polymerizaiotn is carried put in two slurry reactors operating in series, by varying the hydrogen concentration in the two reactors.
- the organic material component B) is selected from liquid paraffin, solid paraffin; wax; and mineral oil; more preferably the organic material component B) is a mineral oil; even more preferably the organic material component B) is white mineral oil (CAS 8042-47-5).
- the organic material component B) is selected from liquid paraffin, solid paraffin; wax; and mineral oil; more preferably the organic material component B) is a mineral oil; even more preferably the organic material component B) is white mineral oil (CAS 8042-47-5).
- composition of the present disclosure can be obtained with a process comprising the step of mixing component A) and component B) to perform a granulation in a mixer.
- composition of the present disclosure can be used in the formation of a microporous membrane having good Gurley permeability and good mechanical properties.
- a method most suitably employed for obtaining the microporous membrane in accordance with the present disclosure comprises the steps of mixing organic material component B) with component A), heating and melting the mixture, extruding the melt into a sheet, orientating the sheet biaxially, either simultaneously or sequentially, and then extracting the liquid with a volatile solvent (dichloromethane for example).
- a volatile solvent dichloromethane for example
- the membrane can be subjected to a heat-setting process, this last step enhances the dimensional stability and prevents shrinkage or wrinkle formation upon heating, which is important for safety and control of the final performance.
- microporous membrane obtained with the composition of the present disclosure shows a good Gurley permeability, measured according to ISO 5636.
- the porosity measures according to the method described in the examples is particularly good, the porosity preferably ranges from 30.0% to 60.0%, more preferably from 33.0% to 51.0%; more preferably from 34.0% to 45.0%.
- the puncture resistance of microporous membrane normalized for 20pm ranges from 700 g/20pm to 1200 g/20pm; preferably from 750 g/20pm to 150 g/20pm; more preferably from 800 g/20pm to 998 g/20pm
- a further object of the present disclosure is the use of ultra-high-molecular- weight propylene homopolymer containing up to 1.0 wt% of ethylene derived units component A) for producing a microporous membrane.
- a further object of the present disclosure is the microporous membrane preferably obtainable with the above process, having Gurley permeability normalized to 20pm thickness measured according to ISO 5636 lower than 1200 s/100ml720pm, preferably lower than 1100 s/100m/20pm more preferably lower than 850 s/100m/20pm.
- a further object of the present disclosure is the microporous membrane obtainable with the above described process.
- Xylene Solubles fraction has been measured according to ISO 16 152 - 2005; with solution volume of 250 ml, precipitation at 25°C for 20 minutes, 10 of which with the solution in agitation (magnetic stirrer), and drying at 70°.
- Tm melting points of the polymers
- the weighted sample was sealed into aluminium pans and heated to 200°C at 20°C/minute.
- the sample was kept at 200°C for 2 minutes to allow a complete melting of all the crystallites, then cooled to 5°C at 20°C/minute.
- the sample was heated for the second run time to 200°C at 20°C/min. In this second heating run, the peak temperature (Tp,m) was taken as the melting temperature. 13 C NMR of homopolymer and propylene/ethylene copolymers
- the tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmTpp (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm).
- the melt strength is measured according to ISO 16790-2005 by Haul-off Melt Strength Meter produced by Geottfert Maschinenstoff Pruefmaschinen, Germany. This system measures the extensional properties of polymer melts by drawing a vertical melt strand at a constant pull-off speed or with a linear or exponentially accelerating velocity.
- the HAUL-OFF system measures the force needed to elongate the strand, and calculates elongation stress, draw ratio and apparent elongation rate and viscosity. Polymer is melt and plasticized through a capillary rheometer, then is extruded from a hole die with a 1 mm of diameter, 30 mm of length and 180° inlet angle. The test is performed at 250°C.
- the distance from the capillary outlet to the center of the transducer pulley is 150 mm.
- the monofilament is stretched at each temperature test applying an acceleration equal to 6 mm/s 2 and, passing through an angular transducer, its tension is measured.
- the draw ratio (dimensionless value) and force (cN) values are recorded as the final result in addition to the entire curve.
- the value of the melt strength is considered the maximum force value of the curve.
- Tensile Modulus is measured according to ISO 527-2, and ISO 1873-2 on compression sample
- the solid catalyst used in the following examples was prepared according to the Example 10 of the International Patent Application WO 00/63261.
- Tri ethylaluminium (TEAL) was used as co-catalyst and dicyclopentyldimethoxysilane as external donor, with the weight ratios indicated in Table 1.
- the polymerization run is carried out in continuous mode in a series of two reactors equipped with devices to transfer the product from one reactor to the one immediately next to it.
- the two reactors are liquid phase loop reactors.
- Propylene is the solvent, hydrogen is used as molecular weight regulator.
- the gas phase (propylene, ethylene and hydrogen) is continuously analyzed via gaschromatography.
- the polymer of example 1 (component A) has been mixed with white mineral oil (CAS 8042-47- 5) sold by Kukdong component B).
- Gurley permeability has been measured according to ISO 5636, the value has been normalized for 20pm sheet.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP23163207 | 2023-03-21 | ||
| PCT/EP2023/077550 WO2024193835A1 (en) | 2022-11-07 | 2023-10-05 | Polypropylene resin compositon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4683953A1 true EP4683953A1 (en) | 2026-01-28 |
Family
ID=85772132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23783446.0A Pending EP4683953A1 (en) | 2023-03-21 | 2023-10-05 | Polypropylene resin compositon |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP4683953A1 (en) |
| CN (1) | CN120731230A (en) |
-
2023
- 2023-10-05 EP EP23783446.0A patent/EP4683953A1/en active Pending
- 2023-10-05 CN CN202380094490.3A patent/CN120731230A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN120731230A (en) | 2025-09-30 |
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